Ethylene Raw Materials and Production Economics

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9 Ethylene Raw Materials and Production

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Economics J. G. FREILING, C. C. KING, and J. NEWMAN The Lummus Co., Bloomfield, N. J. 07003

The outlook for ethylene demand in the next decade is for continued strong growth with total new construction for the period forecasted at almost 100 billion pounds per year requiring the erection of about 100 plants. Careful attention will have to be given to proper selection of feedstocks if these huge investments are to be profitable. This paper discusses the differences relating to the various potential feed materials with respect to product distribution, investment and operating costs and examines the economics of ethylene production for a variety of situations. Both the U.S. and European pictures are covered, with emphasis on the effects of the important variables of feed and byproduct prices, operating severity, and scale. Future trends in feedstock availability and pricing are discussed as well as possible effects of a potential change in the U.S. import quota system and of unleaded gasoline.

*T*he 1970s promise a continuation of the rapid worldwide growth in ethylene demand witnessed in the past decade. To meet the challenge of such growth successfully, it will be vital for planners to have a thorough understanding of the factors entering into the ethylene production economics. Perhaps the most important of these factors involves the raw material employed for this purpose and the by-product volumes and prices. In this connection we discuss the product distributions from potential various feedstocks and current trends in feedstock selection, illustrating the significant role feedstocks play in the ethylene commercial picture. In addition, the effects on production economics of the factors of plant size and severity of operation are investigated. A

158 In Origin and Refining of Petroleum; McGrath, H., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1971.

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159

Ethylene Matreials and Production

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Much of the information represents an updating of material presented in two papers related to the ethylene area prepared by the Lummus Co. in 1968 (J, 2). In addition, however, particular emphasis is given to possible new developments in the United States which could dramatically affect raw material choices. We explore the effects that a potential change in the import quota system and a move to lead free gasoline could have on the U.S. ethylene industry. Ethylene

Demands

The outlook for ethylene demand in the next decade is one of continued strong growth. Based on our discussions with several ethylene producing and consuming companies, we feel that the projections shown in Table I, which presents estimated annual ethylene demands for the 1970-80 period, are realistic and if anything, somewhat conservative. In the United States ethylene demand is expected to go from 15.7 billion pounds in 1970 to over 35 billion pounds in 1980—a compounded annual growth rate of about 8%%. In Western Europe annual demand will grow by some 17 billion pounds between 1970 and 1980 from the Table I.

Ethylene Demands—1970 to 1980 Billion Lbs/Yr

Year

1970

1975

1980

Location U.S.A. W. Europe Japan Other (Ex. Eastern Bloc)

15.7 12.0 5.3 2.0

24.7 19.5 9.6 6.7

35.5 29.0 14.8 16.7

Total

35.0

60.5

96.0

1970 level of about 12 billion pounds. An even more vigorous growth is predicted for the ethylene industry in Japan. Demand there will nearly triple in the next decade to almost 15 billion pounds by 1980 for a growth rate of nearly 11% per year. The totals shown indicate that over-all annual demand ( Ex. Eastern Bloc) for ethylene will grow by 62 billion pounds by 1980 corresponding to about a 10% per year growth. To satisfy the increases in demand in the next decade, ethylene plant construction will have to continue at a brisk pace. Table II gives our estimates of plant growth and the inside battery limits (ISBL) capital investments required. An approximate 69 billion lbs/year increase in plant capacity must be installed in the period to meet the increase in demand. An additional 25 billion lbs will probably be installed to retire

In Origin and Refining of Petroleum; McGrath, H., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1971.

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ORIGIN A N D R E F I N I N G OF P E T R O L E U M

obsolete and uneconomic units. Thus, the total new construction for the decade will be ca. 94 billion lbs/year of ethylene. This will require the erection of about 100 plants. The associated order of magnitude ISBL battery limits investment for these plants will be around 4 billion dollars ( current basis ) for the surveyed areas. Needless to say, the 1970s will require the careful selection of feedstocks by producers and the close cooperation of both producers and engineer-contractors to ensure that the challenge of such large investments can be profitably met. Feedstock and By-Product Effects The U.S. ethylene industry has been based primarily on the cracking of ethane and propane derived from natural gas. The quantities and liquid contents of U.S. natural gases have been such as to permit substantial quantities of these light hydrocarbons to be recovered for use as economically attractive ethylene feedstocks. In Europe and Japan, however, naphthas have been generally the available and preferred feeds to pyrolysis. The fight hydrocarbons produce only minor amounts of by-products, while naphtha and heavier feeds produce substantial quantities of propylene, butadiene, and aromatics. Thus, while in the United States these products are obtained generally from other routes at present, in Europe and Japan ethylene production serves as a major source of these chemicals. As discussed in greater detail later, by-product outlet considerations can play an important role in feedstock selection, and by-product realizations can have a major effect on the ethylene production economics. Table II. Location

Growth of Ethylene Industry—1970 to 1980 Other (Ex. W. Eastern U.S.A. Europe Japan Bloc) Total

New demand, billions of lbs/yr Equivalent capacity, billions of lbs/yr Existing capacity to be retired, billions of lbs/yr Total new capacity needed, billions of lbs/yr Approx. no. of plants Approx. total new ISBL plant investment, M M $

20

17

10

15

62

22

19

11

17

69

12

6

3

4

25

34 28

25 25

14 16

21 30

94 99

1200

1100

600

1000

3900

In Origin and Refining of Petroleum; McGrath, H., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1971.

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FREILING ET A L .

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Production

161

Ethylene Materials and Production

Patterns

Table III gives a range of the possible feedstocks that can be used to produce ethylene and the kinds and amounts of by-products that can be made from them. For our purposes we have selected a constant basis of 1 billion lbs/year ethylene production. The feedstocks illustrated in Table III include ethane, propane, η-butane, a full range naphtha, a light gas oil, and a heavy gas oil. The yields reflect high severity conditions with recycle cracking of ethane in all cases. For propane feed, propane recycle cracking has been included as well. The figures for the naptha case pertain to a straight run C / 3 6 0 ° F (TBP) cut point material; the light gas oil included here is a 386/633°F ( ASTM ) end point atmospheric distillate, and the heavy gas oil is repre­ sentative of a light vacuum distillate with TBP cut point extending to 850 °F. The once-through ethylene yields for these three feeds are 27, 23, and 21 wt % , respectively. Note that ethane recycle increases the yield of ethylene over the once-through figure. This of course means that less feed can be used for the same ethylene production. With the naphtha feed, ethane recycle cracking increases the 27 wt % once-through yield on feed to 31.4 wt % , reducing feed requirements by 16%. 5

As one progresses from ethane through heavier, lower hydrogen content feedstocks the yield of ethylene decreases and causes feed re­ quirements to increase markedly. For example, cracking heavy gas oil would require slightly over three times the amount of feed (per lb of ethylene ) that is needed for ethane cracking. The extra feed required for heavier stocks is, of course, distributed among the various by-products. The total amount of by-products increases as feed molecular weight is increased. The heavier, lower hydrogen content feedstocks are more suited to over-all olefins production. Note especially the increase in the ratio of propylene/ethylene as the feedstocks become heavier. With ethane feed very little propylene is made, about 0.04 lb/lb ethylene whereas for the high severity propane cracking shown, the ratio is 0.39. For the heavier feeds the ratio tends to increase and reaches 0.57 for high severity cracking of the heavy gas oil. Interestingly, η-butane makes more propylene by-product than does this high severity naphtha operation and almost the same amount of propylene as does the heavy gas oil. Of course, operating at a lower severity will increase propylene/ethylene ratio. In view of the predicted tight worldwide propylene supply/demand situation (3) the yield of propylene as well as that of ethylene will be an important consideration in feedstock selection. As for the other by-products produced via cracking heavier feeds, the general trend is toward reduced off-gas production and increased pro-

In Origin and Refining of Petroleum; McGrath, H., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1971.

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ORIGIN A N D R E F I N I N G OF P E T R O L E U M

Table III.

Feed and Product 1000 MM Lbs/Yr

Feedstock Feed rate, 10 lbs/yr 6

Products, 10 lbs/yr Off Gas Ethylene (polymer grade) Propylene (chemical grade) C fraction butadiene butylenes/butanes C /400°F naphtha 400°F + fuel oil

Ethane

Propane

1311.8

2379.6

211.7 1000.0 38.4

713.7 1000.0 385.0

17.6 7.5 36.6 —

76.1 32.6 142.9 29.3

1311.8

2379.6

24.9 20.0

80.9 18.2

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6

4

5

Total products B T X aromatics in pyro. Naphtha 10 lbs/yr Hydrogen in feed, wt % 6

duction of butadiene, pyrolysis naphtha, and fuel oil. There is a marked increase in the 4 0 0 ° F + fuel oil product when cracking gas oils. This will offer an important incentive for the ethylene producer to develop additional market outlets or uses for gas oil pyrolysis products. One route, providing for burning increased quantities of the material in the pyrolysis heaters, would sharply reduce, if not eliminate, the amount of fuel normally imported to gas oil plants. Other possible outlets for this material would be as carbon black or coker feed. As discussed later, the aromatics produced by pyrolysis may take on added significance in the United States if the much talked about plans to remove lead from U.S. gasoline materialize. It is generally agreed that the values of aromatics as "process" octane improvers will be enhanced. Heavier feeds produce more aromatics-rich pyrolysis naphtha, with the full range naphtha yielding significantly more aromatics than any other feed considered in Table III. The concentration of BTX in the C ,/400°F fraction from naphtha cracking (at 27 wt % once-through ethylene) is about 65 wt % . This puts the yield of these aromatics at nearly 16 wt % of feed naphtha. Of course, to recover these aromatics the pyrolysis naphtha is usually hydro-treated first and then sent to aromatics extraction. The nonaromatic pyrolysis raffinate is highly naphthenic and is an excellent feedstock to catalytic reforming for production of additional aromatics. r

In Origin and Refining of Petroleum; McGrath, H., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1971.

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163

Ethylene MateHals and Production

FREILING E T A L .

Summary for Various Feedstocks

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Ethylene Production n-Butane

Full-Range Naphtha

Light Gas Oil

Heavy Gas Oil

2764.6

3193.6

3789.1

4108.1

592.4 1000.0 564.3

578.7 1000.0 470.5

453.0 1000.0 537.5

482.3 1000.0 568.1

84.1 348.5 112.0 63.3

119.5 133.2 771.9 119.8

147.0 177.0 739.6 735.0

150.9 177.8 727.0 1002.0

2764.6

3193.6

3789.1

4108.1

320.5

276.0

13.3

13.0

51.3

501.7

17.3

15.0

Alternative

Feedstock Economics

Investments. The approximate inside battery limits (ISBL) invest­ ments for billion lb/year ethylene plants using the various feedstocks are given in Table IV. Thefigurespresented represent a project getting underway on the U.S. Gulf Coast in early 1970. The investments of course could vary somewhat with the specific location and time of con­ struction. They are based on production of propylene of only chemical grade and do not include pyrolysis gasoline hydro-treating nor butadiene or aromatics extraction facilities. The costs indicate a significant increase as the feeds become heavier. Table IV.

Approximate ISBL Plant Investments

1000 MM Lbs/Yr Ethylene Production FullRange Feedstock

Ethane

Light

Heavy

Propane τι-Butane Naphtha Gas Oil Gas Oil

Approximate ISBL cost, M M J 35 40 42 43 50 52 Feed and By-Product Pricing Basis. Table V shows the feed and by-product price basis used in our economic calculations. Separate price structures are shown for the United States and Europe. For each case the by-product prices are assigned two values: (a) fuel value and (b) premium or chemical value. Pricing the by-products on each basis yields two values of ethylene production costs for each case considered. These

In Origin and Refining of Petroleum; McGrath, H., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1971.

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ORIGIN A N D R E F I N I N G OF P E T R O L E U M

Table V .

Feedstock

Assumed Feed

Ethane

Propane

1.0

1.0

Location Unit cost, £/\b

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By-products Unit Values j £/lb Off-gas Propylene (chemical grade) C4 fraction butadiene butylènes/butanes C /400°F naphtha 400°F + fuel oil 5

Fuel Value 0.48-0.74 0.41 0.40 0.41 0.38 0.35

values represent the maximum range of production costs one might expect under extremes of by-product valuation. A producer might be in an "overlap" situation—i.e., some by-products can be sold at premium prices whereas others might only command fuel value. In that case, the ethylene production cost would fall somewhere between the two extremes mentioned above. In setting the prices for the premium cases, we have incorporated a "sliding" price scale on some by-products; hence, a range of prices appears in some rows of Table V. These price variations reflect differences in the composition of a particular by-product which result from cracking different feedstocks. By way of example, the aromatics content of a pyrolysis naphtha depends on the specific feedstock from which it is derived. The premium price of the particular pyrolysis naphtha thus depends on its BTX concentration. The nonaromatic content of the pyrolysis naphtha is valued the same as naphtha. Further details can be found in Table VI. The prices and values shown must be considered as illustrative only rather than as an attempt to predict the future. They are based generally on literature data averages and on discussions with a number of chemical and refining companies. While the figures used are generally representative of present price levels, in some cases a simplification is used—e.g., taking ethane, propane, and butane prices at 1 cent/lb. Effect of Feed and Value of By-Products on Production Costs. The ethylene production costs for the six feedstocks considered and the relevant by-product dispositions are shown in Tables VII and VIII.

In Origin and Refining of Petroleum; McGrath, H., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1971.

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F R E i L i N G E T AL.

and By-Product Values Full Range Naphtha

τι-Butane

Heavy Gas Oil

Full Range Naphtha

Europe

U.S.A. 1.0

1.6

1.1

1.1

1.0

0.75

Europe

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Heavy Gas Oil

Light Gas Oil

Premium or Chemical Value

Fuel Value

Premium or Chemical Value

0.73-2.84 2.75

1.05-1.06 0.89

1.40-1.45 2.0

5.0 1.30-2.20 1.30-2.10 0.50

0.86 0.87 0.81 0.59

4.0 1.0 1.05-1.30 0.59

Table VI.

Further Details on Product Unit Values

Off-Gas A. Taken at fuel value, φ/ΜΜ BTU(LHV) B. Taken at prem. value contained H , ^f/MSCF methane & other, φ/ΜΜ BTU(LHV) 2

Butylenes/Butanes A. Taken at fuel value, φ/lb B. Taken at prem. value butylènes, φ/lb butanes, φ/lb

U.S.A.

Europe

21

45

30 21

30 45

0.41

0.87

2.3 1.0

1.0 0.87

—unextracted state—

Butadiene

C /400°F naphtha 0.81 A. Taken at fuel value, φ/lb 0.38 B. Taken at prem. value untreated and before separation, based following values as finished products: benzene, φ/gai 25 85% of toluene, φ/goi !7 U.S. values C aromatics, fi/gal 19 -valued as naphthanonaromatics 5

8

Table VII presents the data for ethane, propane, η-butane, full range naphtha, and heavy gas oil cases for the United States, while Table VIII shows the naphtha, light gas oil, and heavy gas oil based on a European situation.

In Origin and Refining of Petroleum; McGrath, H., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1971.

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The figures are based on: ( a ) 1 billion lbs/year ethylene production. (b) OSBL (outside battery limits) plant investment taken at ap­ proximately 25% of ISBL plant investment. (c) Operating costs include direct labor, supervision, plant over­ heads, maintenance, utilities, catalysts and chemicals, local taxes, insur­ ance, and depreciation. (d) Return on investment taken at 20% before income taxes on total plant investment. (e) Sales and startup expenses, working capital, spare parts, and general corporate administrative overheads are not included. Effect of Feedstock

Table VII.

1000 MM Lbs/Yr U.S.A.

Location

Propane

Ethane

Feedstock Costs, φ/Lb Ethylene Feed cost Operating cost By-product credits

Premium Fuel Premium Fuel By-products By-products By-products By-products 1.31 1.16 (0.88)

1.59 Production cost (ex. return on investment) Return on investment 0.88 Total production cost fi/lb ethylene

2.47

1.31 1.16 (0.20)

2.38 1.32 (2.34)

2.38 1.32 (0.61)

2.27

1.36

3.09

0.88

1.00

1.00

3.15

2.36

4.09

Table VIII.

Effect of Feedstock 1000 MM Lbs/Yr

Location Feedstock

Full Range Naphtha

Costs, t/Lb. Ethylene

Premium By-products

Fuel By-products

Feed cost Operating cost By-products credits

3.19 1.68 (3.45)

3.19 1.68 (1.95)

1.42

2.92

1.08

1.08

2.50

4.00

Production cost (ex. return on investment) Return on investment Total production cost ff/lb. Ethylene

In Origin and Refining of Petroleum; McGrath, H., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1971.

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Ethylene Materials and Production

Further details on the operating cost basis assumed are given in Table IX. A number of conclusions can be drawn from Tables VII and VIII concerning feedstock choice. These are discussed below. In the United States. With premium by-product prices prevailing, ethylene can be made from η-butane more cheaply than from either ethane or propane, assuming these light hydrocarbon feeds would be all available at 1^/lb. With fuel valued by-products in the United States, ethane is the preferred feedstock. on Ethylene Production Costs Ethylene Production U.S.A. τι-Butane

Full Range Naphtha

Heavy Gas Oil

Premium Fuel Premium Fuel Premium Fuel By-products By-products By-products By-products By-products By-products 2.77 1.29 (3.07)

2.77 1.29 (0.76)

5.11 1.35 (4.13)

5.11 1.35 (0.92)

4.52 1.76 (4.53)

4.52 1.76 (1.23)

0.99

3.30

2.33

5.54

1.75

5.05

1.05

1.05

1.08

1.08

1.30

1.30

2.04

4.35

3.41

6.62

3.05

6.35

on Ethylene Production Costs Ethylene Production Europe Light Gas Oil

Heavy Gas Oil

Premium By-products

Fuel By-products

Premium By-products

Fuel By-products

4.14 2.16 (3.75)

4.14 2.16 (2.27)

3.08 2.28 (3.95)

3.08 2.28 (2.48)

2.55

4.03

1.41

2.88

1.25

1.25

1.30

1.30

3.80

5.28

2.71

4.18

In Origin and Refining of Petroleum; McGrath, H., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1971.

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Table IX.

Basis for Operating Costs

Utilities Fuel, t/MM BTU(LHV) Power, jé/KWH Steam, (H.P.), φ/Μ lbs Cooling water, φ/Μ gal Direct labor, $/yr./shift position Supervision & plant overheads Maintenance, material, & labor Insurance & local taxes Depreciation Return on investment

U.S. A.

Europe

21 45 0.7 1.1 65 110 2.5 3.0 44,000 25,000 —115%/yr of direct labor— 4^%/yr ISBL + 2^%/yr OSBL 2%/yr (ISBL + OSBL) 10%/yr ISBL + 5%/yr OSBL 10%/yr after 50% corporate taxes

At current price levels, heavier feeds in the United States are not competitive with light hydrocarbon feeds. With U.S. naphtha at 1.6^/lb (10^/gal), the ethylene production costs from this feed ranges about 40-70% higher than costs associated with lighter feeds, assuming pre­ mium by-product values. The differences are even greater with fuel by­ product values prevailing. The current unattractiveness of heavier feeds in the United States notwithstanding, ethylene can be made more cheaply from 1.1^/lb heavy gas oil than from 1.6^/lb naphtha even though a gas oil plant is more expensive and requires more feed. This applies for both premium and fuel by-product cases. Even so, ethylene production costs with gas oil feed are about 25-50% higher than costs with light hydrocarbon feeds. In Europe. With either premium or fuel by-product prices prevail­ ing, naphtha is very marginally the preferred feedstock. Heavy gas oil appears to be an interesting feed possibility at current price levels. Although the ethylene production cost with this feed is slightly higher than with naphtha, the difference is so small that it could be wiped out by a naphtha price increase of less than 0.1^/lb. The conclusions advanced here depend on the feed prices as listed in Table V. The effect of feed price variations is very important in ascer­ taining the most profitable route to ethylene. We discuss this question later. Another point to emphasize is that the economics presented in Tables VII and VIII are "ideal," i.e., they do not reflect start-up and sales expenses, possible production delays, and other factors which would increase the cost of making ethylene above the figures shown. Effect of Scale Plant size is important in ethylene production economics as in most manufacturing operations. The economy of scale for ethylene stems

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basically from the reduction in capital requirements per unit of ethylene produced. This reduction in unit investment is a direct result of the well-known fact that as capacity increases, total plant investment does not go up in the ratio of capacities but rather in the ratio of capacities to some exponent which generally is less than one. Figure 1 shows the effect of variations in plant size on the investment per unit ethylene capacity. Table X shows the effect of capacity on ethylene production costs for a European naphtha plant. Note that investment-based items such as return on investment and depreciation and others included in operating cost decrease, per unit of ethylene produced, as plant size gets larger.

40 I 400

I 600

I 800

I 1000

1 1200

PLANT SIZE, MM LBS./YR. OF ETHYLENE PRODUCED

Figure 1.

Effect of capacity on on-site investment (naphtha feed)

In Origin and Refining of Petroleum; McGrath, H., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1971.

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The ethylene production cost for a 1000 M M lb/yr plant is 2.5^/lb (this figure also appears in the European naphtha column of Table VIII). For a 20% increase in capacity to 1200 M M lb/yr, the ethylene production cost drops to about 2.4^/lb. For a decrease in capacity of 60% from 1000 to 400 M M lb/yr, the production cost increases by almost 30% to 3.2^/lb. Table X shows that the advantages of scale diminish drastically as capacity is increased. By way of example, the decrease in production cost going from 400 to 700 M M lb/yr is about 0.5^/lb C ; the next 300 M M lb/yr increment (to a 1000 M M lb/yr) brings only a 0.2^/lb. reduc­ tion in production costs.

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2

Table X.

Effect of Plant Capacity on Production Costs

Basis: Naphtha Feedstock at European Location; Premium By-Product Values 1000 700 Capacity, MM lbs/yr ethylene 400

1200

Costs, φ/lb. of ethylene Feed cost Operating cost Subtotal By-product credits Production cost Return on investment Total production cost

3.19 1.62 4.81 (3.45) 1.36 1.01 2.37

3.19 2.03 5.22 (3.45) 1.77 1.45 3.22

3.19 1.80 4.99 (3.45) 1.54 1.20 2.74

3.19 1.68 4.87 (3.45) 1.42 1.08 2.50

The other point to keep in mind is that as plant sizes become larger, the cost of the feedstock becomes a larger percentage of the total pro­ duction costs. It is evident that with the trend to larger plants, the small producer is at a distinct disadvantage in that his costs, per unit ethylene, are higher than for the bigger producers. To sell his product competitively he may be forced to accept a lower than desired profit, or even go out of business. Of course, he can retire his small unit and get back into things with a new big unit. The trend has been to larger plants. In recent years, plants world­ wide have been averaging about 650 M M lb/yr, and the outlook is for them to get even larger. We may see a billion lb/yr average size plant in the near future, especially in the United States. ICI recently com­ pleted a year of continuous ethylene production following a very smooth initial start-up of their billion lb/yr plant in Wilton, England. Shell is in the process of bringing a 1.2 billion lb/yr cracker on stream at their Deer Park, Tex. location. Plant sizes can get larger, but bigness has negative factors associated with it as well. A single line plant of 1.5 billion lbs/yr capacity is possible today, but beyond this it is doubtful that unit investment costs would be

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F R E i L i N G E T AL.

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reduced significantly. Limitations in commercially proven compressor designs, the need to field fabricate the major fractionating towers, etc., would act to limit further important cost savings. The "super large plant" would also be more vulnerable to market uncertainties and "eggs in one basket" risk. In this latter connection both contractors and owner management play a joint role in ensuring reliability of operation and avoidance of unscheduled shutdowns. Great strides have been made in this area with better design, inspection and safety procedures, and by the use of improved maintenance and operating techniques. Effect of Severity Let us look at changes in cracking severity and how they affect feed requirements, by-product production, and ethylene production costs. We have selected the once-through yield of ethylene as a convenient means of representing severity. Yield Pattern. Table XI presents a feed/product summary for a naphtha based billion lb/yr ethylene plant at various severities of 23, 25, and 27 wt % ethylene (once-through basis). The naphtha feed is the same one as referred to earlier ( see Table III ). It is immediately apparent that feed requirements are increased at lower severities for a given ethylene production rate. Also, production of olefin by-products increases as severity decreases. Note especially the 36% increase in propylene production as severity is dropped from 27% ethylene to 23% ethylene. Butadiene production goes up somewhat, while butylènes production jumps by over 100% going from 27 to 23% ethylene. Table X L

Feed and Product Summary for Various Severities

1000 MM Lbs/Yr Ethylene Production from Naphtha Once-Through Ethylene, wt % Naphtha feed rate, 10 lbs/yr Products, 10 lbs/yr Off-gas Ethylene (polymer grade) Propylene (chemical grade) C fraction butadiene butylenes/butanes C /400°F naphtha 400°F + fuel oil Total products B T X aromatics in pyro. naphtha, 10 lbs/yr 6

23

25

27

3728.6

3437.6

3193.6

524.5 1000.0 639.0

552.0 1000.0 569.5

578.7 1000.0 470.5

153.0 272.5 1055.0 84.6 3728.6

138.0 198.5 880.0 99.6 3437.6

119.5 133.2 771.9 119.8 3193.6

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501.7

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In Origin and Refining of Petroleum; McGrath, H., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1971.

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ORIGIN A N D R E F I N I N G OF P E T R O L E U M

Another glance at Table XI reveals that gas make is reduced when severity is dropped while B T X aromatics produced remains about the same over the severities studied. Since the amount of C / 4 0 0 ° F produced increases at lower severities, the percent BTX in the C / 4 0 0 ° F fraction decreases in order to retain a relatively constant aromatics production. As cracking severity is increased, the tendency to form tars, polynuclear aromatics, coke, etc., is increased. A convenient measure of this tendency is the hydrogen content of the C + produced. When this hydrogen content goes below 7%, cokes and tars are rapidly laid down in the heater and subsequent quench facilities thereby severely curtailing run lengths. Thus, maximum severity is set by this hydrogen limit. The 27% ethylene case of Table XI represents such a maximum for the naphtha in question. Of course, with feeds less rich in hydrogen—e.g., gas oils—the 7% hydrogen limit is reached at ethylene yields lower than 27%. Severity then, is an effective vehicle to vary the product distribution according to specific needs. This type of flexibility can be, and is often built into the design of an ethylene plant and adds relatively little to the cost of the plant. Another simple way to vary the by-product-to-ethylene ratio is to vary the extent of recycle cracking of ethane. Production Costs. The effect of varying severity on ethylene production costs is given in Figure 2. Both premium and fuel by-product situations are covered. The curves apply to a billion lb/yr European naphtha pyrolysis plant. With fuel by-product values, the cost of producing ethylene increases as once-through severity decreases from 27 wt % . For example, at 27 wt % ethylene, the production cost is 4.0^/lb; at 23 wt % the cost rises to over 4.2^/lb. This is primarily a result of more feed being downgraded to fuel at lower severity. More interesting, however, is the result when premium by-product values apply. Here we see that the production cost dips through a minimum at about 25% severity. This may be explained by noting that as severity drops, by-product credits increase owing to increased olefins production so that by-products credits minus feed costs increase, even while feed requirements go up. This tends to lower production costs. On the other hand, the investment and operating costs tend to increase as severity drops—this tends to raise production costs. The net effect is a minimum in production costs at about 2.45^/lb of ethylene. Implicit in Figure 2 are changes in investments and utility costs associated with severity changes. For the naphtha plant at 1000 M M lb/yr capacity, the investment in going from 27% severity to 23% is increased by about 1.9 MM$; the utilities cost increases by about 0.5 MM$/yr. 5

5

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5

In Origin and Refining of Petroleum; McGrath, H., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1971.

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FREILING ET A L .

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Ethylene Materials and Production

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Feed Availability and Effect of Feed Prices Earlier we showed that variations in the prices for feedstocks could have an important influence in determining the best ethylene route. Now we quantify these effects and tie this into current trends regarding feedstock availabilities which would influence the question. Europe. The demand for naphtha for petrochemical feed purposes in Europe continues to rise strongly. As a result, the prices for this commodity have risen over the past several years. Increased use of light North African crudes, providing a higher proportion of gasoline and potential petrochemical naphtha, has retarded but not stopped the rise in naphtha prices. It would be foolhardy to attempt to predict definitively the level of naphtha prices at some particular future date. However, additional 4.3

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23

24

25

26

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ONCE-THROUGH SEVERITY. WT. % ETHYLENE

Figure 2. Effect of severity on European ethylene production costs (1000 MM lbs/yr ethylene production from naphtha feed)

In Origin and Refining of Petroleum; McGrath, H., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1971.

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ORIGIN A N D R E F I N I N G OF P E T R O L E U M

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Figure 3. Effect of feedstock price on European ethylene production costs (1000 MM lbs/yr ethylene production; pre­ mium value by-products) naphtha can be produced for petrochemical purposes in European re­ fineries by practicing a more intensive degree of crude oil processing. Installation of more conversion equipment both in new refinery con­ struction and as additions to existing hydroskimming facilities is already a trend. The production of more naphtha by providing new conversion units would, of course, make the additional naphtha more costly. In this connection a number of studies both our own and others (4) have at­ tempted to determine the cost of incremental naphtha production. These indicate that in typically sized European hydroskimming refinery (oper­ ating on either Libyan or Arabian crudes) gasoline plus petrochemical naphtha yields can be increased by about 50% by installation of catalytic cracking. Based on today's prices for the other refinery products, the cost

In Origin and Refining of Petroleum; McGrath, H., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1971.

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Ethylene Materials and Production

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of the incremental naphtha obtained in this manner would be about 1^/lb (including a return on the investment required for the new facilities). Similarly an even larger increase in naphtha boiling range material would be feasible if hydrocracking rather than cat cracking were employed. Adding a hydrocracker could increase the base hydroskimmer's gasoline plus naphtha yield by almost 150%. The average cost for this much larger quantity of additional naphtha would be about 1.3^/lb. Figure 3 presents the effect of feed price on ethylene production costs in a billion lb/yr European plant for naphtha, light gas oil, and heavy gas oil feedstocks based on premium by-product valuations. From this display it can be seen that a 0.1^/lb increase in naphtha price from 1.0 to 1.1^/ lb would raise the ethylene production cost from 2.5 to 2.8^/lb. If such a movement did occur, heavy gas oil at current 0.75^/lb levels (based on equivalent heavy fuel oil adjusted for viscosity considerations and vacuum distillation costs) would become competitive with naphtha. This "breakeven" relationship between heavy gas oil (actually light vacuum gas oil) is shown more conveniently in Figure 4. The breakeven price defines the unit price one could afford to pay for the gas oil to realize the same ethylene production cost as for a naphtha feed. If for a given naphtha price, the gas oil can be obtained at a price below the indicated gas oil breakeven price, gas oil would be the more attractive feed. If the gas oil can only be obtained at a price above the breakeven, naphtha would be the desired feed. Thus, with naphtha at, say, 1^/lb, the heavy gas oil would have to be priced below 0.7^/lb to be more profitable than naphtha as a cracking feed, assuming premium by-products prevail. Valuing the by-products as fuel has only a slight effect on the breakeven levels. The curves cross as nonaromatics in the pyrolysis gasoline have been valued the same as naphtha feed. Thus, at today's naphtha prices and by-product markets, pyrolysis of light vacuum gas oil appears closely competitive with naphtha for ethylene production. The breakeven curve for light ( atomospheric ) gas oil is given in Figure 5. If light gas oil can be disposed of at prevailing middle distillate prices of about 1.1^/lb, naphtha would have to sell at 1.4 to 1.5^/lb for the gas oil to become attractive. Therefore, pyrolysis of atmospheric gas oil will not be ordinarily attractive. United States. The U.S. ethylene industry has been based mainly on pyrolysis of light hydrocarbons, predominately ethane and propane recovered from natural gas. Essentially all the ethane recovered is used as pyrolysis feed, whereas only about one quarter of the propane is used for this purpose. The remainder is mostly consumed in the L P G market.

In Origin and Refining of Petroleum; McGrath, H., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1971.

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ORIGIN A N D R E F I N I N G OF P E T R O L E U M

Recent cold winters plus increased demands for petrochemical feed­ stocks have reversed an oversupply situation on the natural gas liquids to one where demand appears to be outpacing supply. In view of the above, various sources predict price increases for natural gas liquids for petrochemical use (5, β ) . Let us look at the pre­ dicted magnitudes of these possible price increases and their effect on ethylene production costs. One of the sources predicts that ethane prices will reach 1.1—1.3^/lb and propane prices 1.2-1.4^/lb on the Gulf Coast in the mid 1970's. Figure 6 indicates the ethylene production costs from various feed­ stocks in a U.S. billion lbs/yr ethylene plant based on premium valued by-products. If the predicted ethane and propane increases did in fact

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1.4

Figure 4. Breakeven prices for heavy gas oil feed vs. naphtha feed in Europe (1000 MM lbs/yr ethylene production; pre­ mium and fuel value by-products)

In Origin and Refining of Petroleum; McGrath, H., et al.; Advances in Chemistry; American Chemical Society: Washington, DC, 1971.

9.

177

Ethylene Materials and Production

F R E i L i N G ET AL.

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